EP0123482B2 - La dispersion de particules et l'empêchement de leur dépôt à l'aide de copolymères d'acide acrylique - Google Patents
La dispersion de particules et l'empêchement de leur dépôt à l'aide de copolymères d'acide acrylique Download PDFInfo
- Publication number
- EP0123482B2 EP0123482B2 EP84302527A EP84302527A EP0123482B2 EP 0123482 B2 EP0123482 B2 EP 0123482B2 EP 84302527 A EP84302527 A EP 84302527A EP 84302527 A EP84302527 A EP 84302527A EP 0123482 B2 EP0123482 B2 EP 0123482B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- acrylic acid
- weight percent
- copolymer
- use according
- particulate matter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000013618 particulate matter Substances 0.000 title claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 229920002126 Acrylic acid copolymer Polymers 0.000 title description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 80
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 52
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 vinyl aromatic compounds Chemical class 0.000 claims abstract description 15
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 14
- 239000004927 clay Substances 0.000 claims abstract description 11
- 239000000498 cooling water Substances 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims description 36
- 229920002125 Sokalan® Polymers 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 10
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 10
- 239000011236 particulate material Substances 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 22
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 22
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 20
- 239000002270 dispersing agent Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 239000005995 Aluminium silicate Substances 0.000 description 18
- 235000012211 aluminium silicate Nutrition 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 239000011550 stock solution Substances 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 229920001519 homopolymer Polymers 0.000 description 7
- 230000005764 inhibitory process Effects 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 244000104757 Viola obliqua Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 208000004434 Calcinosis Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000533950 Leucojum Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000004443 bio-dispersant Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(II) bromide Substances [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 229960001781 ferrous sulfate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
Definitions
- This invention concerns the use of acrylic acid copolymer for combating particulate matter formation and dispersing particulate matter in an aqueous system.
- This invention more particularly concerns the use of water soluble, low molecular weight copolymers of acrylic acid to disperse inorganic particulate matter and/or to inhibit the precipitation of inorganic particulate matter, such as common hardness ion salts, in aqueous systems.
- Much of the water used in recirculating cooling water systems and water cooled industrial heat exchangers supplied from rivers, lakes, ponds and the like contains high concentrations of suspended inorganic particulate materials such as mud, silt and clay.
- the cooling effect is achieved by evaporating a portion of the water circulating through the tower. This evaporation results in the concentration of the suspended materials in the water. These materials settle in locations of low flow rates and cause corrosion, frictional losses and inefficient heat transfer.
- Water used in cooling systems and water-cooled heat exchangers also contains dissolved salts of hardness ions, such as calcium and magnesium. These salts can precipitate from solution and lead to the formation of scale on the heating surfaces of the cooling systems or exchangers.
- the most common deposit found in cooling water systems is calcium carbonate. Calcium carbonate has a relatively low solubility in water. This solubility decreases with increasing pH, temperature and concentration. Calcium sulfate is also likely to be encountered in cooling water systems. Calcium sulfate may result from the addition of sulfuric acid to raw water to control calcium carbonate scale. While calcium sulfate is more soluble than calcium carbonate, the solubility limit of calcium sulfate can also be easily exceeded resulting in its precipitation from solution.
- High molecular weight polyacrylates and polyacrylamides have been used to agglomerate fine particles of mud and silt into a loose floc to reduce the accumulation of these materials in pipes and heat exchanger tubes.
- these flocs tend to settle in cooling tower basins which then require frequent cleaning for their removal.
- U.S. Patent No. 2,783,200 is directed to a process for conditioning sludge or precipitates in boiler feed water by adding polyacrylic acid or polymethacrylic acid with, and without, inorganic phosphates.
- Copolymers of sodium polyacrylate and polymethacrylate, having undisclosed compositions and high molecular weights, are disclosed as being as effective as sodium polyacrylate homopolymer to treat internal boiler water.
- U.S. Patent No. 3,085,916 relates to a method for removing mud and silt from cooling water by using high molecular weight (greater than 100,000) polymers of acrylic acid or methacrylic acid, their salts, or copolymers formed from at least 50 mole percent acrylic or methacrylic acid with other copolymerizable monomers.
- High rather than low, molecular weight copolymers are taught as being generally more effective as mud and silt flocculants.
- the patent is silent, however, on the use of low molecular weight acrylic polymers or copolymers as dispersants for mud and silt in aqueous systems.
- U.S. Patent No. 3,578,589 is directed to a method for treating cooling water deposits using a nonionic surfactant and acrylic acid or methacylic acid polymers, salts thereof and copolymers of such salts.
- the molecular weight of the copolymers is disclosed as ranging from about 4,000 to about 95,000 while the preferred polymethacrylic acid or sodium polymethacrylate is disclosed as having a molecular weight ranging from 5,000 to 15,000.
- U.S. Patent No. 4,008,164 relates to inhibiting calcium deposits in water using copolymers of acrylic acid and low levels of methyl acrylate where the copolymer has a molecular weight ranging from 3,000 to 20,000 and preferably 6,000 to 8,000. A molar excess of acrylic acid to methylacrylate of at least 3:1 and preferably 4:1 to 5:1 is required. The preferred copolymer has a molecular weight ranging from 6,000 to 8,000.
- Canadian Patent No. 1,097,555 also relates to a process for inhibiting calcium sulfate, calcium carbonate and barium sulfate scale by the addition of copolymers of acrylic acid having molecular weights ranging from 1,000 to 25,000 and preferably 6,000 to 8,000. A molar excess of at least 3:1 and preferably 4:1 to 5:1 acrylic acid to methacrylic acid is disclosed.
- U.S. Patent No. 4,029,577 is directed to a process for controlling the formation of scale and/or suspended solid matter in aqueous systems by introducing copolymers of acrylic acid or a water-soluble salt thereof, and hydroxy lower alkyl (C 2 -C 6 ) acrylate moieties, or water soluble salts thereof, in a molar ratio of about 34:1 to about 1:4.
- the copolymers disclosed have molecular weights ranging from 500 to 1,000,000.
- Australian Patent No. 59,137 relates to inhibiting or modifying scale formation on the heat transfer surfaces of apparatus for the distillation or evaporation of sea water or other waters containing dissolved mineral salts using co- or ter-polymers formed from at least one monomer containing acid or potential acid groupings, the co- or ter-polymers having a molecular weight in the range of 1,000 to 50,000, preferably about 15,000 to about 25,000.
- references relating to methods of treating water with polyacrylic acid-containing additives include: U.S. Patent Nos. 3,293,152; 3,579,455; 3,663,448; 3,699,048; 3,766,077; 4,004,939; 4,209,398; 4,303,568; 4,326,980; Canadian Patent No. 1,057,943; and German Offeng. 2,344,498.
- inorganic particulate matter can be effectively dispersed in aqueous systems by the introduction of water soluble, copolymers of acrylic acid and selected hydrophobic comonomers where the molecular weight of the copolymer is from 2,000 to 5,000 weight average molecular weight.
- water soluble copolymer comprising 85 to 97 weight percent of acrylic acid units and 15 to 3 weight percent of hydrophobic comonomer comprising one or more of (C 2 to C8)-alkyl acrylates, (C, to C, 3 )-alkyl methacrylates and vinyl aromatic compounds, and having a weight average molecular weight of 2,000 to 5,000, for combating the formation of inorganic particulate matter in an aqueous system and for dispersing inorganic particulate matter present in an aqueous system.
- the hydrophobic comonomer preferably comprises ethyl acrylate.
- the weight average molecular weight is preferably 2,500 to 5,000, more preferably about 3,000.
- a preferred copolymer comprises 93 to 97, more preferably about 95, weight percent of acrylic acid units and 7 to 3, more preferably about 5 weight percent of hydrophobic comonomer.
- Preferred copolymers comprise about one unit of ethyl acrylate per unit of acrylic acid polymer chain.
- the copolymer may be used to disperse, for example, calcium carbonate or clay in an aqueous slurry.
- the above copolymer can be a superior dispersant for inorganic particulates and an effective anti-precipitant scale inhibitor for common hardness ion salts in aqueous systems.
- Known products possessing high anti-precipitant activity have generally been deficient in their ability to disperse particulate matter.
- Figure 1 represents a graphical illustration of the kaolin dispersancy of the acrylic acid-hydrophobic copolymers as a fucntion of their weight average molecular weight
- Figure 2 represents a graphical illustration of the kaolin dispersancy of acrylic acid-ethyl acrylate copolymers, having about one unit of ethyl acrylate per chain of acrylic acid, as a function of their weight average molecular weight.
- the present invention may be carried out by adding the copolymer to an aqueous system containing suspended inorganic particulate matter and common hardness ion salts.
- the hydrophobic comonomers useful in the preparation of the copolymers for use in this method include lower alkyl acrylates, having 2 to 8 carbon atoms in the alkyl group, lower alkyl methacrylates, having 1 to 8 carbon atoms in the alkyl group and vinyl aromatic compounds.
- suitable comonomer include ethyl and butyl acrylate, methyl methacrylate and ethyl methacrylate.
- Suitable vinyl aromatic monomers include styrene and alkyl substituted styrene. Mixtures of one or more of these hydrophobic comonomers may be used to form the acrylic acid copolymer. These comonomers must be copolymerizable with and soluble in acrylic acid monomer or a mutual solvent.
- U.S. Patent No. 4,314,004 is directed to one suitable copolymer synthesis method and this method requires a specific concentration range of a copolymerization initiator and a specific molar ratio range of the initiator concentration and the concentration of certain metal salts to obtain the desired low molecular weight copolymers useful in the present invention.
- the preferred copolymerization initiators are peroxide compounds such as ammonium persulfate, potassium persulfate, hydrogen peroxide and t-butyl hydroperoxide.
- the preferred concentration range of the initiator is between about 1 to about 20 weight percent based on the weight of monomers.
- the metal salts used to regulate molecualr weight preferably include cuprous and cupric chloride or bromide, cupric sulfate, cupric acetate, ferrous and ferric chloride, ferrous sulfate and ferric and ferrous phosphate.
- the molar ratio of the copolymerization initiator to the metal salt is preferably between about 40:1 to about 80:1.
- the copolymers of acrylic acid useful in this invention are preferably prepared in water at a copolymer concentration of about 40 to about 50 percent based on total weight of solution.
- isopropanol is used as the molecular weight regulator as well as the reaction solvent.
- the reaction solvent may also be an aqueous mixture of isopropanol containing at least 40 weight percent isopropanol.
- the copolymerization initiator is a free radical initiator such as hydrogen peroxide, sodium persulfate, potassium persulfate, or benzoyl peroxide.
- the copolymerization is carried out under pressure at a temperature of 120 to 200°C.
- the concentration of the copolymer in the solvent is preferably 25 to 45 percent based on the weight of the total solution.
- the free radical copolymerization initiator is ammonium, sodium or potassium persulfate, hydrogen peroxide or t-butyl hydroperoxide.
- the preferred concentration of the initiator is between 0.2 and 10 weight percent based on monomers.
- the polymerization temperature is preferably between 20 and 65°C and the concentration of the copolymers in the aqueous solvent is between 25 to 55 weight percent based on total solution weight.
- a number of copolymers were prepared from about 80 weight percent to about 99 weight percent acrylic acid monomer and from about one weight percent to about 20 weight percent hydrophobic comonomer.
- the weight average molecular weight of the copolymers was varied from about 1,350 to about 8,000 based on polyacrylic acid polymer standards as determined by standard aqueous gel permeation chromatographic techniques.
- the number of comonomer units per acrylic acid polymer chain was calculated.
- the weight average molecular weight of the copolymer is decreased, the number of polymer chains per gram of polymer solids increases.
- copolymers were then evaluated for their ability to disperse a common inorganic particulate material according to the following test method.
- Figure 2 illustrates the dispersancy of the acrylic acid/ethyl acrylate copolymers (Examples 5-11) formed from one unit of ethyl acrylate per chain of acrylic acid.
- This Figure shows the same drop off in dispersancy at one ppm. copolymer concentration with copolymers having Mw below about 2,500.
- the composite of dispersancy for the 1 ppm. and 10 ppm. copolymer concentrations shows that a maximum dispersancy occurs at about 3,000 Mw which corresponds to the preferred copolymer composition of about 95 weight percent acrylic acid and about 5 weight percent ethyl acrylate. It is believed that the incorporation of about one unit of hydrophobic comonomer per chain of acrylic acid results in a copolymer having preferred performance as comapared to other ratios of hydrophobic comonomer units per chain.
- Example 7 The results at 10 ppm. confirm the screening test results presented in Tables II and III.
- the preferred copolymer of this invention (Example 7) was found to be equivalent to the high molecular weight homopolymer (Example 33) and much better than the low molecular weight homopolymer (Example 27) at 10 ppm. At 5 ppm. and 20 ppm., the copolymer of Example 7 was also better than the low molecular weight homopolymer (Example 27) and about equivalent to the higher molecular weight homopolymer (Example 33).
- the anti-precipitation activity of the preferred acrylic acid-ethyl acrylate copolymer for common hardness ion salts was also evaluated and compared with an effective dispersant high Mw h 9 mopolyacrylic acid polymer (Example 33) and the best dispersant low Mw polyacrylic acid (Example 27).
- the test methods used to determine calcium sulfate and calcium carbonate precipitate inhibition are also disclosed in U.S. Patent No. 4,326,980.
- Stock Solution A contained 11.1 grams/liter calcium chloride adjusted to pH 7.0.
- Stock Solution B contained 14.2 grams/liter sodium sulfate adjusted to pH 7.0.
- Stock Solution C contained 2.45 g/I calcium chloride adjusted to pH 8.5.
- Stock Solution D contained 2.48 g/I Na 2 C0 3 adjusted to pH 8.5.
- the sample was then diluted to 50 ml with deionized water and then 3 ml of 50% sodium hydroxide was added followed by Ca+2 indicator.
- the solution was then titrated with EDTA to a purple-violet end point and the calcium carbonate inhibition was calculated as follows:
- the copolymers used in this invention exhibit effective dispersancy for inorganic particulate matter and precipitation inhibition for common hardness ion salts in aqueous systems.
- test results demonstrate the drop-off in antiprecipitation activity of the acrylic acid copolymers having weight average molecular weights less than about 2500 and greater than about 5000.
- the copolymers are effective dispersants for concentrated slurries of calcium carbonate and kaolin clay.
- Kaolin clay and calcium carbonate are used as fillers in plastics, rubbers, and paper, as pigments for paint and rubber, and as paper coatings to provide brightness and gloss.
- kaolin clays and calcium carbonate are shipped, stored, and applied as high solids content aqueous slurries.
- the clay slurries typically contain about 60 to 70% clay solids.
- the particle size of the kaolin clays in the slurries is usually about 2 microns or less in diameter.
- the calcium carbonate slurries typically contain about 60 to 75% or more calcium carbonate solids.
- the slurries viscosity be as low as possible to permit pumping and spraying of the slurry and to permit the slurry to flow after extended storage.
- the cost to manufacture and the concentration of the dispersant in the slurry should be as low as possible to effectively and economically reduce the viscosity of the slurry to manageable levels.
- the viscosity of the slurry without the addition of a dispersant would be in excess of 50 Pas (50,000 centipoise).
- Low molecular weight polyacrylic acid polymers are effective as dispersants for such slurries.
- the dispersant concentration was raised by 0.025 weight percent while keeping the calcium carbonate solids concentration at 75% by adding 0.84 grams of the 10% dispersant solution and 0.63 grams of calcium carbonate to the slurry in the pint jar.
- the new slurry was mixed for 2 minutes and the viscosity was measured. This was repeated until a 0.1 qO weight percent dispersant containing slurry was formed and measured.
- Table VII The results of this test are presented in Table VII.
- the table illustrates that the preferred acrylic acid-ethyl acrylate copolymer is an effective dispersant for high solids content calcium carbonate slurries.
- the pH and viscosity (Brookfield RV viscometer at 20 rpm) was then measured. Following this, the concentration of the dispersant was increased by 0.025 weight percent while keeping the concentration of the clay solids constant at 70% by adding 0.88 grams of the 10% dispersant solution and 2.05 grams of kaolin to the slurry in the jar. The new slurry was mixed for 2 minutes and the viscosity of the slurry was remeasured. This was repeated until the level of dispersant in the slurry was 0.200 weight percent based on kaolin. The results are provided in Table VIII.
- Table VIII illustrates that the preferred acrylic acid-hydrophobic copolymer of this invention is an effective dispersant for concentrated aqueous kaolin slurries.
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- Chemical & Material Sciences (AREA)
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Developing Agents For Electrophotography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
- Colloid Chemistry (AREA)
- Organic Insulating Materials (AREA)
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Claims (12)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT84302527T ATE24308T1 (de) | 1983-04-15 | 1984-04-13 | Die dispergierung von teilchen und die verhuetung von deren ablagerung mittels akrylsaeurekopolymeren. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/485,559 US4517098A (en) | 1983-04-15 | 1983-04-15 | Method of dispersing inorganic materials in aqueous systems with low molecular weight acrylic acid copolymers |
US485559 | 1995-06-07 |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0123482A2 EP0123482A2 (fr) | 1984-10-31 |
EP0123482A3 EP0123482A3 (en) | 1985-01-23 |
EP0123482B1 EP0123482B1 (fr) | 1986-12-17 |
EP0123482B2 true EP0123482B2 (fr) | 1990-07-04 |
Family
ID=23928621
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84302527A Expired - Lifetime EP0123482B2 (fr) | 1983-04-15 | 1984-04-13 | La dispersion de particules et l'empêchement de leur dépôt à l'aide de copolymères d'acide acrylique |
Country Status (13)
Country | Link |
---|---|
US (1) | US4517098A (fr) |
EP (1) | EP0123482B2 (fr) |
JP (1) | JPS6034798A (fr) |
AT (1) | ATE24308T1 (fr) |
AU (2) | AU2678384A (fr) |
BR (1) | BR8401734A (fr) |
CA (1) | CA1217692A (fr) |
DE (1) | DE3461707D1 (fr) |
DK (1) | DK169470B1 (fr) |
FI (1) | FI78889C (fr) |
MX (2) | MX165357B (fr) |
NO (1) | NO164015C (fr) |
ZA (1) | ZA842788B (fr) |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IN161206B (fr) * | 1983-06-28 | 1987-10-17 | Goodrich Co B F | |
GB8416454D0 (en) * | 1984-06-28 | 1984-08-01 | Allied Colloids Ltd | Polymer powders |
US4810328A (en) * | 1984-07-13 | 1989-03-07 | Diamond Shamrock Chemicals Company | Method of brown stock washing |
DE3801326A1 (de) * | 1988-01-19 | 1989-07-27 | Asea Brown Boveri | Verfahren zur herstellung einer keramiksuspension |
US5034062A (en) * | 1990-08-23 | 1991-07-23 | Rohm And Haas Company | Use of acid-containing anionic emulsion copolymers as calcined clay slurry stabilizers |
US5153155A (en) * | 1990-12-06 | 1992-10-06 | H. C. Spinks Clay Company Inc. | Clay slurry |
US5320672A (en) * | 1991-12-17 | 1994-06-14 | Whalen Shaw Michael | Associatively dispersed pigments and coatings containing said pigments |
US5449402A (en) * | 1994-02-17 | 1995-09-12 | Whalen-Shaw; Michael | Modified inorganic pigments, methods of preparation, and compositions containing the same |
GB9523247D0 (en) | 1995-11-14 | 1996-01-17 | Allied Colloids Ltd | Dispersants for emulsion paints |
US6379587B1 (en) * | 1999-05-03 | 2002-04-30 | Betzdearborn Inc. | Inhibition of corrosion in aqueous systems |
US6869996B1 (en) | 1999-06-08 | 2005-03-22 | The Sherwin-Williams Company | Waterborne coating having improved chemical resistance |
EP1074293B1 (fr) * | 1999-08-02 | 2005-10-12 | Rohm And Haas Company | Dispersions aqueuses |
US7303794B2 (en) * | 2004-03-31 | 2007-12-04 | Specialty Minerals (Michigan) Inc. | Ink jet recording paper |
US20060003117A1 (en) * | 2004-06-14 | 2006-01-05 | Specialty Minerals (Michigan) Inc. | Ink jet recording paper |
EP1799782B1 (fr) * | 2004-10-08 | 2012-12-12 | The Sherwin-Williams Company | Revetements aqueux auto-reticulants |
US20060094636A1 (en) * | 2004-11-01 | 2006-05-04 | National Starch And Chemical Investment Holding Corp. | Hydrophobically modified polymers |
EP2351803B1 (fr) * | 2008-11-25 | 2018-12-12 | Toppan Printing Co., Ltd. | Liquide de revêtement et stratifié barrière aux gaz |
JP6942658B2 (ja) * | 2018-03-01 | 2021-09-29 | 水ing株式会社 | カルシウム含有排水のカルシウム除去方法及びカルシウム除去設備 |
JP7314179B2 (ja) | 2018-06-25 | 2023-07-25 | ダウ グローバル テクノロジーズ エルエルシー | 分散剤コポリマーを含む自動食器洗浄用配合物 |
WO2021117134A1 (fr) | 2019-12-10 | 2021-06-17 | Kurita Water Industries Ltd. | Copolymères pour la réduction de formation de tartre contenant de l'hydroxyde de magnésium |
JP7183211B2 (ja) * | 2020-02-27 | 2022-12-05 | 栗田工業株式会社 | パルプ製造工程水系のカルシウム系スケール防止剤及びスケール防止方法 |
WO2022049702A1 (fr) | 2020-09-03 | 2022-03-10 | Kurita Water Industries Ltd. | Copolymères acrylates pour la réduction de formation de tartre |
PL440477A1 (pl) | 2022-02-25 | 2023-08-28 | Pcc Exol Spółka Akcyjna | Hydrofobizowany kopolimer akrylowy, sposób jego wytwarzania, jego zastosowanie i farba wodorozcieńczalna zawierająca ten kopolimer |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1052132A (fr) * | 1900-01-01 | |||
US2783200A (en) * | 1951-11-03 | 1957-02-26 | Dearborn Chemicals Co | Sludge conditioning and dispersing agents for boiler water treatment |
GB772775A (en) * | 1954-06-04 | 1957-04-17 | Monsanto Chemicals | A process for treating hard water |
AU5913765A (en) * | 1965-05-20 | 1967-11-23 | Commonwealth Scientific And Industrial Research Organisation | Improvements in agents for preventing scale formation |
US3699048A (en) * | 1969-07-24 | 1972-10-17 | Benckiser Gmbh Joh A | Process of preventing scale and deposit formation in aqueous systems and product |
DE2057008C3 (de) * | 1970-11-20 | 1979-05-10 | Benckiser Gmbh Joh A | Mittel zur Verhinderung von steinbildenden Ablagerungen in wäßrigen Systemen |
GB1414964A (en) * | 1971-10-19 | 1975-11-19 | English Clays Lovering Pochin | Copolymers and their use in the treatment of materials |
US4008164A (en) * | 1974-03-21 | 1977-02-15 | Nalco Chemical Company | Process for scale inhibition |
SU604866A1 (ru) * | 1974-06-06 | 1978-04-30 | Всесоюзный научно-исследовательский институт по креплению скважин и буровым растворам | Способ обогащени глины дл буровых растворов |
JPS532393A (en) * | 1976-06-30 | 1978-01-11 | Nippon Jiyunyaku Kk | Method of preventing water scale in cooling system |
US4136152A (en) * | 1976-08-30 | 1979-01-23 | Betz Laboratories, Inc. | Method for treating aqueous mediums |
DE2643422A1 (de) * | 1976-09-21 | 1978-03-30 | Kurita Water Ind Ltd | Wasserbehandlungsmittel und verfahren zur behandlung von wasser |
US4186027A (en) * | 1976-10-07 | 1980-01-29 | English Clays Lovering Pochin & Company Limited | Processing of kaolinitic clays at high solids |
DE2757329C2 (de) * | 1977-12-22 | 1980-02-07 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von Polymerisaten der Acrylsäure oder Methacrylsäure |
US4314004A (en) * | 1980-06-26 | 1982-02-02 | Ppg Industries, Inc. | Fluorocarbon resin coated substrates and methods of making |
US4326980A (en) * | 1981-02-23 | 1982-04-27 | Betz Laboratories, Inc. | Acrylic copolymer composition inhibits scale formation and disperses oil in aqueous systems |
-
1983
- 1983-04-15 US US06/485,559 patent/US4517098A/en not_active Expired - Lifetime
-
1984
- 1984-04-11 CA CA000451711A patent/CA1217692A/fr not_active Expired
- 1984-04-12 NO NO841454A patent/NO164015C/no unknown
- 1984-04-12 MX MX200994A patent/MX165357B/es unknown
- 1984-04-12 AU AU26783/84A patent/AU2678384A/en not_active Abandoned
- 1984-04-13 DK DK192784A patent/DK169470B1/da not_active IP Right Cessation
- 1984-04-13 JP JP59074804A patent/JPS6034798A/ja active Pending
- 1984-04-13 EP EP84302527A patent/EP0123482B2/fr not_active Expired - Lifetime
- 1984-04-13 FI FI841494A patent/FI78889C/fi not_active IP Right Cessation
- 1984-04-13 DE DE8484302527T patent/DE3461707D1/de not_active Expired
- 1984-04-13 BR BR8401734A patent/BR8401734A/pt not_active IP Right Cessation
- 1984-04-13 AT AT84302527T patent/ATE24308T1/de not_active IP Right Cessation
- 1984-04-13 ZA ZA842788A patent/ZA842788B/xx unknown
-
1988
- 1988-11-10 AU AU25021/88A patent/AU607277B2/en not_active Ceased
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1991
- 1991-10-23 MX MX9101711A patent/MX9101711A/es not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
NO841454L (no) | 1984-10-16 |
US4517098A (en) | 1985-05-14 |
ATE24308T1 (de) | 1987-01-15 |
ZA842788B (en) | 1985-06-26 |
EP0123482A2 (fr) | 1984-10-31 |
EP0123482B1 (fr) | 1986-12-17 |
FI78889B (fi) | 1989-06-30 |
CA1217692A (fr) | 1987-02-10 |
FI841494A (fi) | 1984-10-16 |
AU2678384A (en) | 1984-10-18 |
FI841494A0 (fi) | 1984-04-13 |
BR8401734A (pt) | 1984-11-20 |
FI78889C (fi) | 1989-10-10 |
JPS6034798A (ja) | 1985-02-22 |
AU607277B2 (en) | 1991-02-28 |
DK169470B1 (da) | 1994-11-07 |
MX9101711A (es) | 1993-08-01 |
AU2502188A (en) | 1989-03-02 |
NO164015C (no) | 1990-08-22 |
EP0123482A3 (en) | 1985-01-23 |
DK192784A (da) | 1984-10-16 |
DK192784D0 (da) | 1984-04-13 |
MX165357B (es) | 1992-11-04 |
NO164015B (no) | 1990-05-14 |
DE3461707D1 (en) | 1987-01-29 |
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